Method of preparing ruthenium and osmium carbene complexes

ABSTRACT

Methods of preparing carbene compounds of the formula ##STR1## are disclosed wherein M is Os or Ru; R and R 1  are independently selected from hydrogen and a functional group selected from the group consisting of C 2  -C 20  alkenyl, C 2  -C 20  alkynyl, C 1  -C 20  alkyl, aryl, C 1  -C 20  carboxylate, C 2  -C 20  alkoxy, C 2  -C 20  alkenyloxy, C 2  -C 20  alkynyloxy, aryloxy, C 2  -C 20  alkoxycarbonyl, C 1  -C 20  alkylthio, C 1  -C 20  alkylsulfonyl or C 1  -C 20  alkylsulfinyl; each optionally substituted with C 1  -C 5  alkyl, a halogen, C 1  -C 5  alkoxy or with a phenyl group optionally substituted with a halogen, C 1  -C 5  alkyl or C 1  -C 5  alkoxy; X and X 1  are independently selected from any anionic ligand; and L and L 1  are independently selected from any neutral electron donor, preferably phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine and thioether. Methods for using these carbene compounds to catalyze olefin metathesis reactions are also disclosed.

ORIGIN OF INVENTION

The U.S. Government has certain rights in this invention pursuant to Grant No. CHE-8922072 awarded by the National Science Foundation.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of application Ser. No. 08/282,826 filed on Jul. 29, 1994, now abandoned, which is a continuation-in-part of application Ser. No. 08/106,292, filed Aug. 13, 1993 (now U.S. Pat. No. 5,342,909) which was a divisional of application Ser. No. 07/863,606 filed Apr. 3, 1992 (now U.S. Pat. No. 5,312,940).

BACKGROUND OF THE INVENTION

This invention relates to the synthesis of new ruthenium and osmium metal carbene complex compounds and their use as catalysts in olefin metathesis reactions.

During the past two decades, research efforts have enabled an in-depth understanding of the olefin metathesis reaction as catalyzed by early transition metal complexes. In contrast, the nature of the intermediates and the reaction mechanism for Group VIII transition metal catalysts has remained elusive. In particular, the oxidation states and ligation of the ruthenium and osmium metathesis intermediates are not known.

Many ruthenium and osmium metal carbenes have been reported in the literature (for example, see Burrell, A. K., Clark, G. R., Rickard, C. E. F., Roper, W. R., Wright, A. H., J. Chem. Soc., Dalton Trans., 1991, Issue 1, pp. 609-614). The discrete ruthenium and osmium carbene complexes isolated to date do not exhibit metathesis activity. (Ivin, Olefin Metathesis, pp. 34-36, Academic Press: London, 1983)

SUMMARY OF THE INVENTION

The present invention relates to the synthesis of ruthenium or osmium carbene compounds which can be used to catalyze olefin metathesis reactions.

The carbene compounds of the present invention are the only Ru and Os carbene complexes known to date in which the metal is formally in the +2 oxidation state, have an electron count of 16, and are pentacoordinate. Unlike most metathesis catalysts presently known which are poisoned by functional groups, the carbene compounds of the present invention are stable in the presence of alcohol, thiol, ketone, aldehyde, ester, ether, amine, amide, nitro acid, carboxylic acid, disulfide, carbonate, carboalkoxy and halogen functional groups and may therefore be used in protic or aqueous solvent systems.

Specifically, the present invention relates to carbene compounds of the formula ##STR2## wherein: M is Os or Ru;

R and R¹ are independently selected from hydrogen or a functional group selected from the group consisting of C₂ -C₂₀ alkenyl, C₂ -C₂₀ alkynyl, C₁ -C₂₀ alkyl, aryl, C₁ -C₂₀ carboxylate, C₂ -C₂₀ alkoxy, C₂ -C₂₀ alkenyloxy, C₂ -C₂₀ alkynyloxy, aryloxy, C₂ -C₂₀ alkoxycarbonyl, C₁ -C₂₀ alkylthio, C₁ -C₂₀ alkylsulfonyl or C₁ -C₂₀ alkylsulfinyl;

X and X¹ are independently selected from any anionic ligand; and

L and L¹ are independently selected from any neutral electron donor, preferably phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine and thioether, most preferably trialkylphosphine ligands where at least one of the alkyl groups is a secondary alkyl or a cycloalkyl.

In a preferred embodiment the functional group is substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group.

In a preferred embodiment the phenyl group is substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy.

In one embodiment of the present invention, the carbene compounds can be in the form wherein 2, 3 or 4 of the moieties X, X¹, L and L¹ can be taken together to form a chelating multidentate ligand. In one aspect of this embodiment, X, L, and L¹ can be taken together to form a cyclopentadienyl, indenyl, or fluorenyl moiety.

In a second, preferred embodiment of the present invention, L and L¹ are each trialkyl phosphine ligands where at least one of the alkyl groups is a secondary alkyl or a cycloalkyl. Carbene compounds where L and L¹ ligands are alkyl phosphines where the carbon backbone of at least one alkyl group of the alkyl phosopine is a secondary alkyl or cycloalkyl have been found to possess higher metathesis activity, enabling these compounds to coordinate to and catalyze metathesis reactions between all types of olefins. By contrast, previous metathesis catalysts were only able to catalyze metathesis reactions involving highly strained olefins. As a result, a broad array of metathesis reactions are enabled using the carbene compounds of the present invention that cannot be performed using less reactive catalysts. The carbene compounds of this preferred embodiment and their use in olefin metathesis reactions is described in U.S. patent application Ser. No. 08/282,827, pending entitled HIGH ACTIVITY RUTHENIUM AND OSMIUM METAL CARBENE COMPLEXES FOR OLEFIN METATHESIS REACTIONS, filed the same data as this application and which is incorporated herein by reference.

The ruthenium and osmium carbene compounds may be prepared by reacting a compound of the formula (XX¹ ML_(n) L¹ _(m))_(p), in the presence of solvent, with a cyclopropene of the formula ##STR3## wherein: M, X, X¹, L, and L¹ having the same meaning as indicated above;

n and m are independently 0-4, provided n+m=2, 3 or 4;

p is an integer equal to or greater than 1; and

R² and R³ are independently selected from hydrogen or a functional group selected from the group consisting of C₁ -C₁₈ alkyl, C₂ -C₁₈ alkenyl, C₂ -C₁₈ alkynyl, C₂ -C₁₈ alkoxycarbonyl, aryl, C₁ -C₁₈ carboxylate, C₁ -C₁₈ alkenyloxy, C₂ -C₁₈ alkynyloxy, C₁ -C₁₈ alkoxy, aryloxy, C₁ -C₁₈ alkylthio, C₁ -C₁₈ alkylsulfonyl or C₁ -C₁₈ alkylsulfinyl;

In a preferred embodiment the hydrocarbon is substituted with C₁ -C₅ alkyl, halogen, C₁ -C₃ alkoxy or with a phenyl group.

In a preferred embodiment the phenyl group is substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy.

In one embodiment of the process, X, L, and L¹ are taken together to form a moiety selected from the group consisting of cyclopentadienyl, indenyl or fluorenyl, each optionally substituted with hydrogen; C₂ -C₂₀ alkenyl, C₂ -C₂₀ alkynyl, C₁ -C₂₀ alkyl, aryl, C₁ -C₂₀ carboxylate, C₁ -C₂₀ alkoxy, C₂ -C₂₀ alkenyloxy, C₂ -C₂₀ alkynyloxy, aryloxy, C₂ -C₂₀ alkoxycarbonyl, C₁ -C₂₀ alkylthio, C₁ -C₂₀ alkylsulfonyl, C₁ -C₂₀ alkylsulfinyl; each optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy.

A further method of preparing the compounds of this invention comprises reacting compound of the formula (XX¹ ML_(n) L¹ _(m))_(p) in the presence of solvent with a phosphorane of the formula ##STR4## wherein: M, X, X¹, L, L¹, n, m, p, R, and R¹ have the same meaning as indicated above; and

R⁴, R⁵ and R⁶ are independently selected from aryl, C₁ -C₆ alkyl, C₁ -C₆ alkoxy or phenoxy, each optionally substituted with halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy.

The present invention also pertains to a preferred method of preparing the aforementioned ruthenium and osmium compounds comprising reacting (Ar) MX X¹ !₂ dimer complex with two equivalents of a phosphine ligand and a cyclopropene of the formula ##STR5## in a one step synthesis wherein: M, X and X¹ have the same meaning as indicated above;

Ar is an aromatic compound, preferably a di-, tri-, tetra- or hexa- substituted benzene, most preferably selected from benzene, toluene, xylene, cymene, tetramethylbenzene or hexamethylbenzene; and phosphine ligand is represented by the formula PR⁷ R⁸ R⁹ wherein R⁷, R⁸ and R⁹ are independently selected from substituted and unsubstituted C₁ -C₁₀ alkyl, secondary alkyl, cycloalkyl and aryl.

Another embodiment of the present invention comprises preparing compounds of Formula II and Formula III ##STR6## from compound of Formula I ##STR7## comprising reacting said compound of Formula I, in the presence of solvent, with compound of the formula M¹ Y wherein:

M, R, R¹ X, X¹, L, and L¹ have the same meaning as indicated above, and wherein:

(1) M¹ is Li, Na or K, and Y is C₁ -C₁₀ alkoxide, arylalkoxide, amide or arylamide each optionally substituted with C₁ -C₁₀ alkyl or halogen, diaryloxide; or

(2) M¹ is Na or Ag, and Y is ClO₄, PF₆, BF₄, SbF₆ halogen, B(aryl)₄, C₁ -C₁₀ alkyl sulfonate or aryl sulfonate.

Another embodiment of the present invention is a method of preparing compounds of structures of Formula IV ##STR8## and Formula V ##STR9## from a compound of Formula I ##STR10## comprising reacting a compound of Formula I, in the presence of solvent, with L² wherein:

M, R, R¹, X, and X¹ have the same meaning as indicated above; and

L, L¹, and L² are independently selected from any neutral electron donor, preferably secondary alkyl or cycloalkyl phosphine ligands.

The compounds of Formulae II, III, IV, and V are species of, i.e., fall within, the scope of compounds of Formula I. In other words, certain compounds of Formula I are used to form other compounds of Formula I by ligand exchange. In this case, X and X¹ in Formula I are other than the Y in Formulae II and III that replaces X. Similarly, L and L¹ in Formula I are other than the L² in Formulae IV and V. If any 2 or 3 of X, X¹, L, and L¹ form a multidentate ligand of Formula I, only the remaining ligand moieties would be available for ligand replacement.

The reference above to X, X¹, L, and L¹ having the same meaning as indicated above refers to these moieties individually and taken together to form a multidentate ligand as described above.

DETAILED DESCRIPTION

The ruthenium and osmium carbene complexes of the invention are useful for catalyzing olefin metathesis reactions. The propagating carbene moiety has been found to be stable and continues to polymerize additional aliquots of monomer for a period after the original amount of monomer has been consumed. The propagating carbene moiety has also been found to be stable in the presence of alcohol, thiol, ketone, aldehyde, ester, ether, amine, amide, nitro acid, carboxylic acid, disulfide, carbonate, carboalkoxy and halogen functional groups. Aspects of this invention include the metal carbene compounds, methods for their synthesis, as well as their use as catalysts in a wide variety of olefin metathesis reactions.

The intermediate compounds (XX¹ ML_(n) L¹ _(m))_(p) are either available commercially or can be prepared by standard known methods.

The phosphorane and cyclopropene reactants used in the present invention may be prepared in accordance with the following respective references. Schmidbaur, H. et at., Phosphorus and Sulfur, Vol. 18, pp. 167-170 (1983); Carter, F. L., Frampton, V. L., Chemical Reviews, Vol. 64, No. 5 (1964) which are incorporated herein by reference.

With regard to compounds of Formula I:

alkenyl can include 1 -propenyl, 2 -propenyl; 3-propenyl and the different butenyl, pentenyl and hexenyl isomers, 1,3-hexadienyl and 2,4,6-heptatrienyl, and cycloalkenyl;

alkenyloxy can include H₂ C═CHCH₂ O, (CH₃)₂ C═CHCH₂ O, (CH₃)CH═CHCH₂ O (CH₃)CH═C(CH₃)CH₂ O and CH₂ ═CHCH₂ CH₂ O;

alkoxide can include methoxide, t-butoxide, and phenoxide;

alkoxy can include methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers, cycloalkoxy can include cyclopentyloxy and cyclohexyloxy;

alkoxyalkyl can include CH₃ OCH₂, CH₃ OCH₂ CH₂, CH₃ CH₂ OCH₂, CH₃ CH₂ CH₂ CH₂ OCH₂ and CH₃ CH₂ OCH₂ CH₂ ; and

alkoxycarbonyl can include CH₃ OC(═O); CH₃ CH₂ OC(═O), CH₃ CH₂ CH₂ OC(═O), (CH₃)₂ CHOC(═O) and the different butoxy-, pentoxy- or hexyloxycarbonyl isomers;

alkyl can include primary, secondary and cycloalkyl isomers;

alkylsulfinyl can include CH₃ SO, CH₃ CH₂ SO, CH₃ CH₂ CH₂ SO, (CH₃)₂ CHSO and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers;

alkylsulfonyl can include CH₃ SO₂, CH₃ CH₂ SO₂, CH₃ CH₂ CH₂ SO₂, (CH₃)₂ CHSO₂ and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers;

alkylthio can include, methylthio, ethylthio, and the several propylthio, butylthio, pentylthio and hexylthio isomers;

alkynyl can include ethynyl, 1-propynyl, 3-propynyl and the several butynyl, pentynyl and hexynyl isomers, 2,7-octadiynyl and 2,5,8-decatriynyl;

alkynyloxy can include HC═CCH₂ O, CH₃ C═CCH₂ O and CH₃ C═CCH₂ OCH₂ O;

amide can include HC(═O)N(CH₃)₂ and (CH₃)C(═O)N(CH₃)₂ ;

amine can include tricyclohexylamine, triisopropylamine and trineopentylamine;

arsine can include triphenylarsine, tricyclohexylarsine and triisopropylarsine;

aryl can include phenyl, p-tolyl and p-fluorophenyl;

carboxylate can include CH₃ CO₂ CH₃ CH₂ CO₂, C₆ H₅ CO₂, (C₆ H₅)CH₂ CO₂ ;

cycloalkenyl can include cyclopentenyl and cyclohexenyl;

cycloalkyl can include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl;

diketonates can include acetylacetonate and 2,4-hexanedionate;

ether can include (CH₃)₃ CCH₂ OCH₂ CH₃, THF, (CH₃)₃ COC(CH₃)₃, CH₃ OCH₂ CH₂ OCH₃, and CH₃ OC₆ H₅ ;

"halogen" or "halide", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine;

phosphine can include triphenylphosphine, tricyclohexylphosphine, triisopropylphosphine, trineopentylphosphine and methyldiphenylphosphine;

phosphinite can include triphenylphosphinite, tricyclohexylphosphinite, triisopropylphosphinite, and methyldiphenylphosphinite;

phosphite can include triphenylphosphite, tricyclohexylphosphite, tri-t-butylphosphite, triisopropylphosphite and methyldiphenylphosphite;

secondary alkyl includes ligands of the general formula --CHRR¹ where R and R¹ are carbon moieties;

stibine can include triphenylstibine, tricyclohexylstibine and trimethylstibine;

sulfonate can include trifluoromethanesulfonate, tosylate, and mesylate;

sulfoxide can include CH₃ S(═O)CH₃, (C₆ H₅)₂ SO; and

thioether can include CH₃ SCH₃, C₆ H₅ SCH₃, CH₃ OCH₂ CH₂ SCH₃, and tetrahydrothiophene.

A neutral electron donor is any ligand which, when removed from a metal center in its closed shell electron configuration, has a neutral charge, i.e., is a Lewis base.

An anionic ligand is any ligand which when removed from a metal center in its closed shell electron configuration has a negative charge. An important feature of the carbene compounds of this invention is the presence of the ruthenium or osmium in the formal +2 oxidation state (the carbene fragment is considered to be neutral), an electron count of 16 and pentacoordination. A wide variety of ligand moieties X, X¹, L, and L¹ can be present and the carbene compound will still exhibit its catalytic activity.

A preferred embodiment of the carbene compounds of the present invention is:

A compound of the invention of Formula I wherein:

R and R¹ are independently selected from hydrogen, vinyl, C₁ -C₁₀ alkyl, aryl, C₁ -C₁₀ carboxylate, C₂ -C₁₀ alkoxycarbonyl, C₁ -C₁₀ alkoxy, aryloxy, each optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy;

X and X¹ are independently selected from halogen, hydrogen, diketonates, or C₁ -C₂₀ alkyl, aryl, C₁ -C₂₀ alkoxide, aryloxide, C₂ -C₂₀ alkoxycarbonyl, arylcathoxylate, C₁ -C₂₀ carboxylate, aryl or C₁ -C₂₀ alkylsulfonate, C₁ -C₂₀ alkylthio, C₁ -C₂₀ alkylsulfonyl, C₁ -C₂₀ alkylsulfinyl, each optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy; and

L and L¹ are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, surfoxide, carbonyl, nitrosyl, pyridine or thioether.

A more preferred embodiment of the carbene compounds of the present invention is:

A compound of Formula I wherein:

R and R¹ are independently selected from hydrogen; vinyl, C₁ -C₅ alkyl, phenyl, C₂ -C₅ alkoxycarbonyl, C₁ -C₅ carboxylate, C₁ -C₅ alkoxy, phenoxy; each optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy;

X and X¹ are independently selected from Cl, Br, I, or benzoate, acetylacetonate, C₁ -C₅ carboxylate, C₁ -C₅ alkyl, phenoxy, C₁ -C₅ alkoxy, C₁ -C₅ alkylthio, aryl, and C₁ -C₅ alkyl sulfonate; each optionally substituted with C₁ -C₅ alkyl or a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy;

L, and L¹ are independently selected from aryl or C₁ -C₁₀ alkylphosphine or C₁ -C₅ alkyl, secondary alkyl or cycloalkylphosphine, aryl- or C₁ -C₁₀ alkylsulfonated phosphine, aryl or C₁ -C₁₀ alkylphosphinite, aryl- or C₁ -C₁₀ alkylphosphonite, aryl- or C₁ -C₁₀ alkylphosphite, aryl- or C₁ -C₁₀ alkylarsine, aryl- or C₁ -C₁₀ alkylamine, pyridine, aryl- or C₁ -C₁₀ alkyl sulfoxide, aryl- or C₁ -C₁₀ alkylether, or aryl- or C₁ -C₁₀ alkylamide, each optionally substituted with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy.

A further preferred embodiment of the present invention is carbene compounds of Formula I wherein:

R and R¹ are independently vinyl, H, Me, Ph;

X and X¹ are independently Cl, CF₃ CO₂, CH₃ CO₂, CFH₂ CO₂, (CH₃)₃ CO, (CF₃)₂ (CH₃)CO, (CF₃)(CH₃)₂ CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate; and

L and L¹ are independently PPh₃, P(p-Tol)₃, P(o-Tol)₃, PPh(CH₃)₂, P(CF₃)₃, P(p-FC₆ H₄)₃, pyridine, P(p-CF₃ C₆ H₄)₃, (p-F)pyridine, (p-CF₃)pyridine, P(C₆ H₄ -SO₃ Na)₃, P(CH₂ C₆ H₄ -SO₃ Na)₃, P(^(i) Pr)₃, P(CHCH₃ (CH₂ CH₃))₃, P(cyclopentyl)₃, P(cyclohexyl)₃, P(neopentyl)₃, P(Me)₃, PMe(Ph)₂ and P(neophenyl)₃.

For any of the foregoing described preferred groups of compounds, any 2, 3, or 4 of X, X¹, L, L¹ can be taken together to form a chelating multidentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates. Specific examples include Ph₂ PCH₂ CH₂ PPh₂, Ph₂ AsCH₂ CH₂ AsPh₂, Ph₂ PCH₂ CH₂ C(CF₃)₂ O--, binaphtholate dianions, pinacolate dianions, Me₂ P(CH₂)₂ PMe₂ and --OC(CH₃)₂ (CH₃)₂ CO--. Tridentate ligands include, but are not limited to, (CH₃)₂ NCH₂ CH₂ P(Ph)CH₂ CH₂ N(CH₃)₂. Other preferred tridentate ligands are those in which X, L, and L¹ are taken together to be cyelopentadienyl, indenyl or fluorenyl, each optionally substituted with C₂ -C₂₀ alkenyl, C₂ -C₂₀ alkynyl, C₁ -C₂₀ alkyl, aryl, C₁ -C₂₀ carboxylate, C₁ -C₂₀ alkoxy, C₂ -C₂₀ alkenyloxy, C₂ -C₂₀ alkynyloxy, aryloxy, C₂ -C₂₀ alkoxycarbonyl, C₁ -C₂₀ alkylthio, C₁ -C₂₀ alkylsulfonyl, C₁ -C₂₀ alkylsulfinyl, each optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy. More preferably in compounds of this type, X, L, and L¹ are taken together to be cyclopentadienyl or indenyl, each optionally substituted with hydrogen; vinyl, C₁ -C₁₀ alkyl, aryl, C₁ -C₁₀ carboxylate, C₂ -C₁₀ alkoxycarbonyl, C₁ -C₁₀ alkoxy, aryloxy, each optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy. Most preferably, X, L, and L¹ are taken together to be cyclopentadienyl, optionally substituted with vinyl, hydrogen, Me or Ph. Tetradentate ligands include, but are not limited to O₂ C(CH₂)₂ P(Ph)(CH₂)₂ P(Ph)(CH₂)₂ CO₂, phthalocyanines, and porphyrins.

Carbene compounds of Formula I wherein L and L¹ are alkyl phosphines where at least one alkyl group is either a secondary alkyl or a cycloalkyl. These carbene compounds have been found to be more stable, more reactive to nonsterically strained cyclic alkenes and unreactive to a wider variety of substituents. (Nguyen, S., et al., J. Am. Chem. Soc., 1993, 115:9858-9859; Fu, G., et al., J. Arm Chem. Soc., 1993, 115:9856-9557.)

Specifically, carbene compounds wherein L and L¹ are triisopropyl phosphine or tricyclohexyl phosphine have been found to be stable in the presence of oxygen; moisture, adventitious impurities thereby enabling reactions to be conducted in reagent grade solvents in air (Fn, G., et al., J. Am. Chem. Soc., 1993, 115:9856-9857). Further these carbenes are stable in the presence of alcohol thiol, ketone, aldehyde, ester, ether, amine, amide, nitro acid, carboxylic acid, disulfide, carbonate, carboalkoxy and halogen functional groups. In addition, these carbene can catalyze olefin metathesis reactions on acyclic olefins and strained cyclic olefins.

The most preferred carbene compounds of the present invention include: ##STR11##

^(i) Pr=isopropyl

Cy=cyclohexyl

The compounds of the present invention can be prepared in several different ways, each of which is described below.

The most general method for preparing the compounds of this invention comprises reacting (XX¹ ML_(n) L¹ _(m))_(p) with a cyclopropene or phosphorane in the presence of a solvent to produce a carbene complex, as shown in the equations below. ##STR12## wherein: M, X, X¹, L, L¹, n, m, p, R², R³, R⁴, R⁵, and R⁶ are as defined above. Preferably, R², R³, R⁴, R⁵, and R⁶ are independently selected from the group consisting of C₁ -C₆ alkyl or phenyl.

Examples of solvents that may be using in this reaction include organic, protic, or aqueous solvents which are inert under the reaction conditions, such as: aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Preferred solvents include benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, tetrahydrofuran, diethylether, chlorobenzene, pentane, methanol, ethanol, water, or mixtures thereof. More preferably, the solvent is benzene, toluene, p-xylene, methylenechloride, dichioroethane, dichlorobenzene, tetrahydrofuran, diethylether, pentane, chlorobenzene, methanol, ethanol, or mixtures thereof. Most preferably, the solvent is toluene or a mixture of benzene and methylene chloride.

A suitable temperature range for the reaction is from about -20° C. to about 125° C., preferably 35° C. to 90° C., and more preferably 50° C. to 65° C. Pressure is not critical but may depend on the boiling point of the solvent used, i.e., sufficient pressure is needed to maintain a solvent liquid phase. Reaction times are not critical, and can be from several minutes to 48 hours. The reactions are generally carried out in an inert atmosphere, most preferably nitrogen or argon.

The reaction is usually carried out by dissolving the compound (XX¹ ML_(n) L¹ _(m))_(p), in a suitable solvent, adding the cyclopropene (preferably in a solvent) to a stirred solution of the compound, and optionally heating the mixture until the reaction is complete. The progress of the reaction can be monitored by any of several standard analytical techniques, such as infrared or nuclear magnetic resonance. Isolation of the product can be accomplished by standard procedures, such as evaporating the solvent, washing the solids (e.g., with alcohol or pentane), and then recrystallizing the desired carbene complex. Whether the moieties X, X¹, L, or L¹ are (unidentate) ligands or taken together to form multidentate ligands will depend on the starting compound which simply carries these ligands over into the desired carbene complex.

Under certain circumstances no solvent is needed.

In one variation of this general procedure, the reaction is conducted in the presence of HgCl₂, preferably 0.01 to 0.2 molar equivalents, more preferably 0.05 to 0.1 equivalents, based on XX¹ ML_(n) L¹ _(m). In this variation, the reaction temperature is preferably 15° C. to 65° C.

In a second variation of the general procedure, the reaction is conducted in the presence of ultraviolet radiation. In this variation, the reaction temperature is preferably -20° C. to 30° C.

It is also possible to prepare carbene complexes of this invention by ligand exchange. For example, L and/or L¹ can be replaced by a neutral electron donor, L², in compounds of Formula I by reacting L² with compounds of Formula I wherein L, L¹, and L² are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphorrite, arsine, stibine, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine or thioether. Similarly, X and/or X¹ can be replaced by an anionic ligand, Y, in compounds of Formula I by reacting M¹ Y with compounds of Formula I, wherein Y, X and X¹ are independently selected from halogen, hydrogen, diketonates, or C₁ -C₂₀ alkyl, aryl, C₁ -C₂₀ alkoxide, aryloxide, C₂ -C₂₀ alkoxycarbonyl, arylcalboxylate, C₁ -C₂₀ carboxylate, aryl or C₁ -C₂₀ alkylsulfonate, C₁ -C₂₀ alkylthio, C₁ -C₂₀ alkylsulfonyl, C₁ -C₂₀ alkylsulfinyl, each optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy. These ligand exchange reactions are typically carried out in a solvent which is inert under the reaction conditions. Examples of solvents include those described above for the preparation of the carbene complex.

The carbene compounds of the present invention may also be prepared by a one step synthesis as shown in equation below ##STR13## wherein M, X, X¹, R² and R³ are as defined above. Preferably, R² and R³ are independently selected from the group consisting of C₁ -C₆ alkyl or phenyl. Ar represents an aromatic compound, preferably a di-, tri-, tetra- or hexa- substituted benzene, most preferably benzene, toluene, xylene, cymene, tetramethylbenzene and hexamethylbenzene. R⁷, R⁸ and R⁹ are independently selected from substituted and unsubstituted C₁ -C₁₀ alkyl, secondary alkyl, cycloalkyl and aryl.

Examples of solvents for this reaction include benzene, toluene, xylene and cymene. A suitable temperature range for this reaction is from about 0° C. to about 120° C., preferably 45° C. to 90° C. The reaction may be conducted in the presence of oxygen. However, it is preferred that it is carried out under an inert atmosphere. The reaction is generally performed under atmospheric pressure. Monitoring the progression of the reaction and isolation of the product can be accomplished by any one of a variety of standard procedures known in the art as described above. Typical reaction conditions for this one step synthesis are provided in Example 11.

The carbene compounds of the present invention may be employed in a variety of olefin metathesis reactions such as those described in U.S. Pat. No. 5,312,940 which is incorporated by reference herein and co-pending U.S. patent application, Ser. No. 08/282,827, pending entitled "high Activity Ruthenium and Osmium Carbene Complexes for Olefin Metathesis", entitled HIGH ACTIVITY RUTHENIUM AND OSMIUM METAL CARBENE COMPLEXES FOR OLEFIN METATHESIS REACTIONS, filed on the same date as this application and which is also incorporated herein by reference.

The following examples set forth the synthesis and application of the ruthenium and osmium carbene compounds of the present invention. The following examples also set forth the preferred embodiments of the present invention. Further objectives and advantages of the present invention other than those set forth above will become apparent from the examples which are not intended to limit the scope of the present invention.

The abbreviations Me, Ph, ^(i) Pr, Cy and THF used in the following examples refer to methyl, phenyl, isopropyl, cyclohexyl, and tetrahydrofuran, respectively.

EXAMPLES 1. Method of Preparing Compounds of This Invention From Cyclopropene

A 50 mL Schlenk flask equipped with a magnetic stirbar is charged with (MXX¹ L_(n) L¹ _(m))_(p) (0.1 mmol) inside a nitrogen-filled drybox, Methylene chloride (2 mL) is added to dissolve the complex followed by 25 mL of benzene to dilute the solution. One equivalent of a cyclopropene is then added to the solution. The reaction flask is then capped with a stopper, removed from the box, attached to a reflux condenser under argon and heated at 55° C. The reaction is then monitored by NMR spectroscopy until all the reactants have been converted to the product. At the end of the reaction, the solution is allowed to cool to room temperature under argon and filtered into another Schlenk flask via a cannula filter. The solvent is then removed in vacuo to give a solid. This solid is then washed with a solvent in which the by-product of the reaction is soluble but the desired product is not. After the washing the product, the supernatant is removed and the resulting solid powder is dried in vacuo overnight. Further purification via crystallization can be performed if necessary.

Representative compounds of the present invention which may be prepared in accordance with the procedure described above are exemplified in Table 1.

                                      TABLE 1                                      __________________________________________________________________________      ##STR14##                                                                     Compound name             M X    X.sup.1                                                                             L    L.sup.1                                                                             R R.sup.1                      __________________________________________________________________________     Dichloro-3,3-diphenylvinylcarbene-                                                                       Ru                                                                               Cl   Cl   PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCPh.sub.2                  bis-(triphenylphosphine)ruthenium(II)                                          Dibromo-3,3-diphenylvinylcarbene-                                                                        Ru                                                                               Br   Br   PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCPh.sub.2                  bis-(triphenylphosphine)ruthenium(II)                                          Dichloro-3,3-diphenylvinylcarbene-                                                                       Ru                                                                               Cl   Cl   PPh.sub.2 Me                                                                        PPh.sub.2 Me                                                                        H CHCPh.sub.2                  bis-(methyldiphenylphosphine)ruthenium(II)                                     Dibromo-3,3-diphenylvinylcarbene-                                                                        Ru                                                                               Br   Br   PPh.sub.2 Me                                                                        PPh.sub.2 Me                                                                        H CHCPh.sub.2                  bis-(methyldiphenylphosphine)ruthenium(II)                                     Dichloro-3-methyl-3-phenylvinylcarbene-                                                                  Ru                                                                               Cl   Cl   PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCPhMe                      bis-(triphenylphosphine)ruthenium(II)                                          Dibromo-3-methyl-3-phenylvinylcarbene-                                                                   Ru                                                                               Br   Br   PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCPhMe                      bis-(triphenylphosphine)ruthenium(II)                                          Dichloro-3,3-dimethylvinylcarbene-                                                                       Ru                                                                               Cl   Cl   PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCMe.sub.2                  bis-(triphenylphosphine)ruthenium(II)                                          Bisacetato-3,3-diphenylvinylcarbene-                                                                     Ru                                                                               O.sub.2 CMe                                                                         O.sub.2 CMe                                                                         PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCPh.sub.2                  bis-(triphenylphosphine)ruthenium(II)                                          Acetatochloro-3,3-dimethylvinylcarbene-                                                                  Ru                                                                               O.sub.2 CMe                                                                         Cl   PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCPh.sub.2                  bis-(triphenylphosphine)ruthenium(II)                                          3,3-diphenylvinylcarbene-bis-(trifluoroacetato)-                                                         Ru                                                                               O.sub.2 CCF.sub.3                                                                   O.sub.2 CCF.sub.3                                                                   PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCPh.sub.2                  bis-(triphenylphosphine)ruthenium(II)                                          3,3-diphenylvinylcarbene-η.sup.3 -pinacol bis-(triphenylphosphine)ruth     enium(II)                 Ru                                                                                ##STR15##                                                                               PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCPh.sub.2                  3,3-diphenylvinylcarbene-bis-(tert-butoxy)bis-                                                           Ru                                                                               OCMe.sub.3                                                                          OCMe.sub.3                                                                          PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCPh.sub.2                  (triphenylphosphine)ruthenium(II)                                              3,3-diphenylvinylcarbene-bis-(2-trifluoromethyl-2-propoxy bis-(triphenylph     osphine)ruthenium         Ru                                                                                ##STR16##                                                                           ##STR17##                                                                          PPh.sub.3                                                                           PPh.sub.3                                                                           H CHCPh.sub.2                  __________________________________________________________________________

These are representative examples of the ruthenium complexes. Analogous complexes can be made with osmium.

2. Synthesis of: ##STR18##

In a typical reaction, a 200 mL Schlenk flask equipped with a magnetic stirbar was charged with RuCl₂ (PPh₃)₄ (6.00 g, 4.91 mmol) inside a nitrogen-filled drybox. Methylene chloride (40 mL) was added to dissolve the complex followed by 100 mL of benzene to dilute the solution. 3,3-Diphenylcyclopropene (954 mg, 1.01 equiv) was then added to the solution via pipette. The reaction flask was capped with a stopper, removed from the box, attached to a reflux condenser under argon and heated at 53° C. for 11 h. After allowing the solution to cool to room temperature, all the solvent was removed in vacuo to give a dark yellow-brown solid. Benzene (10 mL) was added to the solid and subsequent swirling of the mixture broke the solid into a fine powder. Pentane (80 mL) was then slowly added to the mixture via cannula while stirring vigorously. The mixture was stirred at room temperature for 1 h and allowed to settle before the supernatant was removed via cannula filtration. This washing procedure was repeated twice more to ensure the complete removal of all phosphine by-products. The resulting solid was then dried under vacuum overnight to afford 4.28 g (98%) of Compound 1 as a yellow powder with a slight green tint. ¹ H NMR (C₆ D₆): δ 17.94 (pseudo-quartet=two overlapping triplets, 1H, Ru═CH, J_(HH) =10.2 Hz, J_(PH) =9.7 Hz), 8.70 (d, 1H, CH═CPh₂, J_(HH) 10.2 Hz). ³¹ P NMR (C₆ D₆): δ 28.2 (s). ¹³ C NMR (CD₂ Cl₂): δ 288.9 (t, M═C, J_(CP) =10.4 Hz) 149.9 (t, CH═CPh₂, J_(CP) =11.58 Hz).

The carbene complex which is the compound formed in the above example is stable in the presence of water, alcohol, acetic acid, HCl in ether and benzaldehyde.

3. Synthesis of: ##STR19##

A 50 mL Schlenk flask equipped with a magnetic stirbar was charged with OsCl₂ (PPh₃)₃ (100 mg, 0.095 mmol) inside a nitrogen-filled drybox. Methylene chloride (2 mL) was added to dissolve the complex followed by 25 mL of benzene to dilute the solution. 3,3-diphenylcyclopropene (18.53 mg, 1.01 equiv) was then added to the solution via pipet. The reaction flask was capped with a stopper, removed from the box, attached to a reflux condenser under argon and heated at 55° C. for 14 h. After allowing the solution to cool to room temperature, all the solvent was removed in vacuo to give a dark yellow-brown solid. Benzene (2 mL) was added to the solid and subsequent swirling of the mixture broke the solid into a fine powder. Pentane (30 mL) was then slowly added to the mixture via cannula while stirring vigorously. The mixture was stirred at room temperature for 1 h and allowed to settle before the supernatant was removed via cannula filtration. This washing procedure was repeated two more times to ensure the complete removal of all phosphine by-products. The resulting solid was then dried under vacuum overnight to afford 74.7 mg of Cl₂ (PPh₃)₂ Os(═CHCH═CPh₂) as a yellow powder (80%). ¹ H NMR (C₆ D₆): δ 19.89 (pseudo-quartet=two overlapping triplets, 1H, Os═CH, J_(HH) =10.2 Hz), 8.23 (d, 1H, CH═CPh₂, J_(HH) =10.2 Hz). ³¹ P NMR (C₆ D₆): δ 4.98 (s).

4. Synthesis of: ##STR20## A 50 mL Schlenk flask equipped with a magnetic stirbar was charged with RuCl₂ (PPh₃)₂ (═CHCH═CPh₂) (100 mg, 0.18 mmol) inside a nitrogen-filled drybox. Methylene chloride (10 mL) was added to dissolve the complex. AgCF₃ CO₂ (24.9 mg, 1 equiv) was weighed into a 10 ml round-bottom flask, dissolved with 3 ml of THF. Both flasks were then capped with rubber septa and removed from the box. The Schlenk flask was then put under an argon atmosphere and the AgCF₃ CO₂ solution was added dropwise to this solution via a gas-tight syringe over a period of 5 min while stirring. At the end of the addition, there was a lot of precipitate in the reaction mixture and the solution turned a fluorescent green color. The supernatant was transferred into another 50 mL Schlenk flask under argon atmosphere via the use of a cannula filter. Subsequent solvent removal in vacuo and washing with penme (10 mL) afforded a green solid powder of the above depicted compound. Yield=92.4 mg (85%). ¹ H NMR (2:2:1 CD₂ Cl₂ :C₆ D₆ :THF-d₈): δ 18.77 (dt, 1H, Ru═CH, J_(HH) =11.2 Hz, J_(PH) =8.6 Hz), 8.40 (d, 1H), CH═CPh₂, J_(HH) =11.2 Hz). ³¹ P NMR (2:2:1 CD₂ Cl₂ :C₆ D₆ :THF-d₈): δ 29.4. ¹⁹ F NMR (2:2:1 CD₂ Cl₂ :C₆ D₆ :THF-d₈): δ 75.8. 5. Synthesis of: ##STR21##

A 50 mL Schlenk flask equipped with a magnetic stirbar was charged with RuCl₂ (PPh₃)₂ (═CH--CH═CPh₂) (100 mg, 0.11 mmol) inside a nitrogen-filled drybox. Methylene chloride (10 mL) was added to dissolve the complex. AgCF₃ CO₂ (49.8 mg, 2 equiv) was weighed into a 10 mL round-bottom flask, dissolved with 4 mL of THF. Both flasks were then capped with rubber septa and removed from the box. The Schlenk flask was then put under an argon atmosphere and the AgCF₃ CO₂ solution was added dropwise via a gas tight syringe over a period of 5 min to the solution of ruthenium compound while stirring. At the end of the addition, there was a lot of precipitate in the reaction mixture and the solution turned into a fluorescent lime green color. The supernatant was transferred into another 50 mL Schlenk flask under argon atmosphere with the use of a cannula filter. Subsequent solvent removal in vacuo and washing with pentane (10 mL) afforded the above depicted compound as a green powder. Yield=102 mg (87%) ¹ H NMR (2:2:1 CD₂ Cl₂ :C₆ D₆ :THF-d₈) δ 19.23 (dt, slightly overlapping) Ru═CH, J_(HH) =11.5 Hz, J_(PH) =5.4 Hz), 8.07 (d, 1H, CH═CPH2, J_(HH) =11.5 Hz). ³¹ P NMR (2:2:1 CD₂ Cl₂ :C₆ D₆ :THF-d₈): δ 28.6. ¹⁹ F NMR (2:2:1 CD₂ Cl₂ :C₆ D₆ :THF-d₈): δ -75.7.

6. Synthesis of: ##STR22##

The reaction between Ru(C₅ Me₅)Cl!₄ and 3,3-diphenylcyclopropene was done under a nitrogen atmosphere. Ru(C₅ Me₅)Cl!₄ (100 mg, 0.092 mmoL) was dissolved in 10 mL of tetrahydrofuran. To this solution was added 3,3-diphenylcyclopropene (350 mg, 1.82 mmol). The resulting solution was stirred at room temperature for 1 h. Petroleum ether (10 mL) was then added to the reaction mixture. The reaction was stirred for an additional 30 min, after which all volatile components were removed from the reaction mixture under vacuum. The crude product was extracted with diethyl ether; volatiles were removed from the filtrate under vacuum to afford a dark colored, oily solid. The crude product was further extracted with petroleum ether; volatiles were removed from the filtrate under vacuum to afford a very dark red-brown oil. Recrystallization from petroleum ether at -40° C. afforded dark crystals. The NMR spectra of the product was consistent with the formulation (C₅ Me₅)RuCl!₂ (═CH--CH═CPh₂).

7. Polymerization of Norbornene Using Compound of Example 2

(PPh₃)₂ Cl₂ Ru═CH--CH═CPh₂ catalyzed the polymerization of norbornene in a 1:8 mixture of CH₂ Cl₂ /C₆ H₆ at room temperature to yield polynorbornene. A new signal, attributed to H.sub.α of the propagating carbene, was observed by ¹ H NMR spectroscopy at 17.79 ppm. Its identity and stability was confirmed by preparing a block polymer with 2,3-dideuteronorbornene and perprotionorbornene. When 2,3-dideuteronorbornene was added to the propagating species, the new carbene signal vanished and then reappeared when perprotionorbornene was added for the third block.

8. Polymerization of Norbornene Using Compound of Example 6

(C₅ Me₅)RuCl!₂ (═CH--CH--CPh₂) (14 mg, 0.030 mmol) was dissolved in 1 mL of perdeuterated toluene under a nitrogen atmosphere. To this was added norbornene (109 mg, 1.16 mmol). The reaction mixture became viscous within minutes as the norbornene polymerized. After 20 h at room temperature a ¹ H NMR spectrum of the reaction mixture was taken, which showed polynorbornene and unreacted norbornene monomer in a ratio of 82:12.

9. Synthesis of: ##STR23##

In a typical reaction, a 100 mL Schlenk flask equipped with a magnetic stirbar was charged with (Ph₃ P)₂ Cl₂ Ru═CH--CH═CPh₂ (3.624 g, 4.08 mmol) and PCy₃ (2.4 g, 2.1 equiv) inside a nitrogen-filled drybox. Methylene chloride (60 mL) was added to dissolve the mixture. The reaction flask was capped with a stopper, removed from the drybox, and stirred under argon overnight during which time the reaction mixture turned red. The reaction mixture was then cannula-filtered under argon into another Scklenk flask. The red filtrate was then concentrated under in vacuo to about 15 mL. Pentane (60 mL) was slowly added to the mixture via cannula while stirring vigorously. A flocculent green solid, consisting mostly starting material, begins to be separated out of the solution when about 40 mL of penme is added. The red supernatant was quickly transferred into another Schlenk flask via cannula filtration and then evaporated to dryness under in vacuo. The remaining red solid was washed with pentane (3×40 mL). To ensure the complete removal of all phosphine by-products, each wash was stirred at room temperature for at least 30 minutes before the supernatant was cannula-filtered away. The resulting solid was then dried under vacuum overnight to afford 3.39 g (ca. 90%) of (Cy₃ P)₂ Cl₂ Ru═CH--CH═CPh₂ as a red powder.

10. Ring-Closing Metathesis of Functionalized Dienes

Table 2 depicts the synthesis of several cycloalkenes from functionalized dienes using Cl₂ Ru(PCy₃)₂ (═CCH═CPh₂) wherein Cy is cyclohexyl. A typical experimental procedure for performing ring-closing metathesis on the diene of entry 8 of Table 2 is as follows.

The diene of entry 8 (0.50 mmol) was added to a homogeneous orange-red solution of 0.01 mmol Cl₂ Ru(PCy₃)₂ (═CCH═CPh₂) in 15 mL of dry benzene under argon. The resulting mixture was then stirred at 20° C. for 5 h, at which time thin layer chromatography showed the reaction to be complete. The reaction was then quenched by exposure to air (until greenish-black, 6 h), concentrated and purified by flash chromatography (0→6% Et₂ O/hexane) to yield dihydropyran as a colorless oil in 86% yield.

                                      TABLE 2                                      __________________________________________________________________________     Catalytic Ring-Closing Metathesis of Dienes (2-4 mol %  Ru!m C.sub.6           H.sub.6, 20° C.)                                                        __________________________________________________________________________                                                  time                                                                               yield                         entry   substrate          product           (hours)                                                                            (%)                           __________________________________________________________________________      1 X = CF.sub.3 2Ot-Bu                                                                  ##STR24##                                                                                         ##STR25##         1 1                                                                               93 91                          3                                                                                      ##STR26##                                                                                         ##STR27##         1  89                             4 n = 0 51 62                                                                          ##STR28##                                                                                         ##STR29##        22  6 40                                                                           78 93 81                       7                                                                                      ##STR30##                                                                                         ##STR31##         2  84                             8                                                                                      ##STR32##                                                                                         ##STR33##         5  86                                     ##STR34##                                                                                         ##STR35##         8  72                            10                                                                                      ##STR36##                                                                                         ##STR37##         1  87                            11                                                                                      ##STR38##                                                                                         ##STR39##         2  85                            __________________________________________________________________________

11. One Step Synthesis of Carbene Compounds

The carbene compounds of the present invention may be prepared in a one step synthesis as illustrated in the reaction sequence below. ##STR40##

In a typical reaction, (Cymene)RuCl₂ !₂ dimer complex (0.53 g, 1.73 mmol Ru) and PCy₃ (0.91 g, 2 equiv) were loaded under inert atmosphere into a 100 mL Schlenk flask equipped with a magnetic stirbar. Benzene(40 mL) was then added followed by 3,3-diphenylcyclopropene(0.33g, 1 equiv). The reaction flask was then attached to a reflux condenser under an inert atmosphere and heated in an oilbath at 83°-85° C. for 6 hours. The solvent was then removed to complete dryness in vacuo and the remaining red solid washed with penme (4×25 mL) under inert atmosphere. The remaining red powder was dried under vacuum for 12 h and stored under an inert atmosphere yielding 1.4 g of Cl₂ Ru(PCy₃)₂ (═CCH═CPh₂) in 88% yield.

12. Carbene Catalyzed Polymerization of 5-Acetoxy-cyclooctene

The carbene compounds of the present invention may be used in the polymerization of nonstrained cyclic olefins such as cyclooctene as depicted in the reaction sequence below. ##STR41## In order to polymerize 5-acetoxy-cyclooctene, a small vial was charged with 2.6 g of degassed 5-acetoxy-cyclooctene and a stirbar. A solution of 15 mg of Cl₂ Ru(PCy₃)₂ (═CCH═CPh₂) in 200 μL of CH₂ Cl₂ was added to the vial under inert atmosphere. The vial was capped and placed in an oil bath at about 48° C. After about 2.5hours, the red-orange solution became noticeably viscous. After about 5.5 hours, the contents of the vial were solid. After 24 hours, the vial was removed from the oil bath and cooled to room temperature. The cap was removed from the vial and 100 μL of ethyl vinylether, 10 mL of chloroform and about 10 mg of 2,6-di-tert-butyl-4-methylphenol(butylated hydroxytoluene) were added to the vial to dissolve the solid, yielding a yellow-orange solution. After about 12 hours of stirring, an additional 20 mL of chloroform was added to the solution. The resulting solution was then poured into about 200 mL of methanol yielding an off-white precipitate. The off-white solid was stirred in the methanol until it appeared free of color. 2.2 g of the resulting white solid was then isolated and dried under vacuum in 85% yield.

While the present invention is disclosed by reference to the preferred embodiments and examples detailed above, it is to be understood that these examples are intended in an illustrative rather than limiting sense, and it is contemplated that modifications within the spirit and scope of the invention will readily occur to those skilled in the art, which modifications are intended to be encompassed within the scope of the appended claims. 

What is claimed is:
 1. A method of preparing a compound of formula ##STR42## the method comprising reacting a compound of the formula (XX¹ ML_(n) L¹ _(m))_(p) with a cyclopropene of the formula ##STR43## in the presence of a solvent wherein: M is Os or Ru;R² and R³ are independently selected from the group consisting of hydrogen, and a substituent group selected from the group consisting of C₁ -C₁₈ alkyl, C₂ -C₁₈ alkenyl, C₂ -C₁₈ alkynyl, C₂ -C₁₈ alkoxycarbonyl, aryl, C₁ -C₁₈ carboxylate, C₁ -C₁₈ alkenyloxy, C₂ -C₁₈ alkynyloxy, C₁ -C₁₈ alkoxy, aryloxy, C₁ -C₁₈ alkylthio, C₁ -C₁₈ alkylsulfonyl and C₁ -C₁₈ alkylsulfinyl; each substituent group optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy; X and X¹ are independently selected from the group consisting of any anionic ligand; L and L¹ are independently selected from the group consisting of any neutral electron donor; n and m are independently 0-4, provided n+m=2, 3 or 4; p is an integer equal to or greater than 1; and any 2 or 3 of X, X¹, L, and L¹ are optionally bonded together to form a chelating multidentate ligand.
 2. The method according to claim 1, wherein R² and R³ are independently selected from the group consisting of C₁ -C₆ alkyl and phenyl.
 3. The method according to claim 1, wherein X and X¹ are independently selected from the group consisting of halogen, hydrogen, diketonates, and a substituent group selected from the group consisting of C₁ -C₂₀ alkyl, aryl, C₁ -C₂₀ alkoxide, aryloxide, C₂ -C₂₀ alkoxycarbonyl, arylcarboxylate, C₁ -C₂₀ carboxylate, aryl or C₁ -C₂₀ alkylsulfonate, C₁ -C₂₀ alkylthio, C₁ -C₂₀ alkylsulfonyl, C₁ -C₂₀ alkylsulfinyl, each substituent group optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy.
 4. The method according no claim 3, wherein X and X¹ are independently selected from the group consisting of Cl, Br, I, and a substituent group selected from the group consisting of benzoate, acetylacetonate, C₁ -C₅ carboxylate, C₁ -C₅ alkyl, phenoxy, C₁ -C₅ alkoxy, C₁ -C₅ alkylthio, aryl, and C₁ -C₅ alkyl sulfonate; each substituent group optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy.
 5. The method according to claim 4, wherein X and X¹ are independently selected from the group consisting of Cl, CF₃ CO₂, CH₃ CO₂, CFH₂ CO₂, (CH₃)₃ CO, (CF₃)₂ (CH₃)CO, (CF₃) (CH₃)₂ CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate.
 6. The method according to claim 1, wherein L and L¹ are independently selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carbonyl, nitrosyl, pyridine and thioether.
 7. The method according to claim 1, wherein L and L¹ are independently selected from the group consisting of arylphosphine, C₁ -C₁₀ alkylphosphine, arylsulfonated phosphine, C₁ -C₁₀ alkylsulfonated phosphine, arylphosphinite, C₁ -C₁₀ alkylphosphinite, arylphosphonite, C₁ -C₁₀ alkylphosphonite, arylphosphite, C₁ -C₁₀ alkylphosphite, arylarsine, C₁ -C₁₀ alkylarsine, arylamine, C₁ -C₁₀ alkylamine, pyridine, arylsulfoxide, C₁ -C₁₀ alkylsulfoxide, arylether, C₁ -C₁₀ alkylether, arylamide, and C₁ -C₁₀ alkylamide; each optionally substituted with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy.
 8. The method according to claim 1, wherein L and L¹ are independently selected from the group consisting of PMe₃, PPh₃, P(p-Tol)₃, P(o-Tol)₃, PMePh₂, PPhMe₂, P(CF₃)₃, P(p-FC₆ H₄)₃, pyridine, P(p-CF₃ C₆ H₄)₃, (p-F)pyridine, (p-CF₃ ) pyridine, P(C₆ H₄ --SO₃ Na)₃, and P(CH₂ C₆ H₄ --SO₃ Na)₃.
 9. The method according to claim 1, wherein 2 of L, L¹, X and X¹ are taken together to form a bidentate ligand selected from the group consisting of bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.
 10. The method according to claim 1, wherein 2 of L, L¹, X and X¹ are taken together to form a bidentate ligand selected from the group consisting of Ph₂ PCH₂ CH₂ PPh₂, Ph₂ AsCH₂ CH₂ AsPh₂, Ph₂ PCH₂ CH₂ C(CF₃)O--, binaphtholate dianions, pinacolate dianions, Me₂ P(CH₂)₂ PMe₂, and --OC(CH₃)₂ (CH₃)₂ CO--.
 11. The method according to claim 1, wherein 3 of L, L¹, and X are taken together to form a tridentate ligand selected from the group consisting of cyclopentadienyl, indenyl, and fluorenyl, each optionally substituted with a substituent group selected from the group consisting of C₂ -C₂₀ alkenyl, C₂ -C₂₀ alkynyl, C₁ -C₂₀ alkyl, aryl, C₁ -C₂₀ carboxylate, C₁ -C₂₀ alkoxy, C₂ -C₂₀ alkenyloxy, C₂ -C₂₀ alkynyloxy, aryloxy, C₂ -C₂₀ alkoxycarbonyl, C₁ -C₂₀ alkylthio, C₁ -C₂₀ alkylsulfonyl, and C₁ -C₂₀ alkylsulfinyl, each optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy.
 12. The method according to claim 11, wherein the tridentate ligand is selected from the group consisting of cyclopentadienyl or indenyl, each optionally substituted with vinyl, C₁ -C₁₀ alkyl, aryl, C₁ -C₁₀ carboxylate, C₂ -C₁₀ alkoxycarbonyl, C₁ -C₁₀ alkoxy, aryloxy, each optionally substituted with C₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy or with a phenyl group optionally substituted with halogen, C₁ -C₅ alkyl or C₁ -C₅ alkoxy.
 13. The method according to claim 12, wherein the tridentate ligand is cyclopentadienyl, optionally substituted with vinyl, Me or Ph.
 14. The method according to claim 1, wherein the solvent is selected from the group consisting of organic, protic, and aqueous solvents.
 15. The method according to claim 1, wherein the solvent is selected from the group consisting of aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, and mixtures thereof.
 16. The method according to claim 15, wherein the solvent is selected from the group consisting of benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, tetrahydrofuran, diethylether, pentate, methanol, ethanol, water, and mixtures thereof.
 17. The method according to claim 15, wherein the solvent is selected from the group consisting of toluene or a mixture of benzene or methylene chloride.
 18. The method according to claim 1, wherein the reaction is carried out at a temperature from about -20° C. to about 125° C.
 19. The method according to claim 18, wherein the reaction is carried out at a temperature from about 35° C. to about 90° C.
 20. The method according to claim 19, wherein the reaction is carried out at a temperature from about 50° C. to about 65° C.
 21. The method according to claim 1, wherein the reaction of (XX¹ ML_(n) L¹ _(m))_(p) with the cyclopropene includes the steps of:(a) dissolving the compound (XX¹ ML_(n) L¹ _(m))_(p) in the solvent to give a (XX¹ ML_(n) L¹ _(m))_(p) solution; and (b) adding the cyclopropene to the (XX¹ ML_(n) L¹ _(m))_(p) solution.
 22. The method according to claim 21, wherein the reaction of (XX¹ ML_(n) L¹ _(m))_(p) with the cyclopropene includes the further steps of heating the cyclopropene/(XX¹ ML_(n) L¹ _(m))_(p) solution mixture produced in step (b).
 23. The method according to claim 1, wherein the reaction of (XX¹ ML_(n) L¹ _(m))_(p) with the cyclopropene includes the steps of:(a) dissolving the compound (XX¹ ML_(n) L¹ _(m))_(p) in the solvent to give a (XX¹ ML_(n) L¹ _(m))_(p) solution; (b) dissolving the cyclopropene in the solvent to give a cyclopropene solution; and (c) adding the cyclopropene solution to the (XX¹ ML_(n) L¹ _(m))_(p) solution.
 24. The method according to claim 1, wherein the reaction of (XX¹ ML_(n) L¹ _(m))_(p) with the cyclopropene is carried out in the presence of HgCl₂.
 25. A method of preparing a compound of formula ##STR44## the method comprising reacting RuCl₂ (PPh₃)₄ with 3,3-Diphenylcyclopropene in the presence of a solvent. 